Recent advances in transition metal phosphide materials:Synthesis and applications in supercapacitors

Supercapacitors(SCs)are considered promising energy storge systems because of their outstanding power density,fast charge and discharge rate and long-term cycling stability.The exploitation of cheap and efficient electrode materials is the key to improve the performance of supercapacitors.As the battery-type materials,transition metal phosphides(TMPs)possess high theoretical specific capacity,good electrical conductivity and superior structural stability,which have been extensively studied to be electrode materials for supercapacitors.In this review,we summarize the up-to-date progress on TMPs materials from diversified synthetic methods,diverse nanostructures and several prominent TMPs and their composites in application of supercapacitors.In the end,we also propose the remaining challenges toward the rational discovery and synthesis of high-performance TMP electrodes materials for energy storage.

Structural phase transition and transport properties in topological material candidate NaZn_(4)As_(3)

We report a comprehensive study on a layered-structure compound of NaZn_(4)As_(3),which has been predicted to be an ideal topological semimetal(TSM) candidate.It is found that NaZn_(4)As_(3) undergoes a structural transformation from high temperature rhombohedral to a low temperature monoclinic phase.The electric resistivity exhibits a metal-to-insulatorlike transition at around 100 K,and then develops a plateau at low temperature,which might be related to the protected topologically conducting surface states.Our first-principles calculation confirms further that NaZn_(4)As_(3) is a topological insulator(TI) for both different phases rather than a previously proposed TSM.The Hall resistivity reveals that the hole carriers dominate the transport properties for the whole temperature range investigated.Furthermore,an obvious kink possibly associated to the structure transition has been detected in thermopower around ~ 170 K.The large thermopower and moderate κ indicate that NaZn_(4)As_(3) and/or its derivatives can provide a good platform for optimizing and studying the thermoelectric performance.

Effect of Modified Vermiculite on the Interface of a Capric Acid-expanded Vermiculite Composite Phase Change Material with Phase Transition Kinetics

A new type of capric acid(CA)-acid expanded vermiculite(AEV) composite phase change material(PCM) with improved adsorption ability and interface adhesive strength was developed. Through the analysis of non-isothermal phase transition kinetics, modified vermiculite was observed to change and affect the phase transformation mechanism of the composite. AEV was treated with hydrochloric acid to improve the specific surface area and micro-pore structure. The surface area measured by BET increased from 81.94 m^2/g for expanded vermiculite(EV) to 544.13 m^2/g for AEV. CA-EV and CA-AEV composite PCMs were prepared by direct impregnation. The non-isothermal phase transition isotherms of CA-EV and CA-AEV were recorded by DSC at different heating rates(1, 5, 10, 15, and 20 ℃/min), which indicated that the phase transition rate increased with the heating rate and the phase transition process changed. Kinetics parameters were analyzed by a double extrapolation method. The activation energy(E) under the original state(E_(α→0)) of CA-AEV and CA-EV was 1 117 kJ/mol and 937 kJ/mol, respectively, and 1 205 kJ/mol and 1 016 kJ/mol under the thermal equilibrium state(E_(β→0)). The most probabilistic mechanism function of CA-AEV satisfied G(α)=α^(2/3), which followed the Mample special rule, and the function of CA-EV satisfied G(α)=[(1+α)^(1/3)-1]~2, which followed the anti-Jander function.

A New Method to Study the Sol-gel Transition Process of Organic/Inorganic Hybrid Materials

The sol-gel transition process of PMMA/SiO2 hybrid materials was first studied by means of the dynamic torsional vibration method. The different stages of the transition can be described by the change of torque. The temperature-dependent measurement of the gel time（ tg ） gives the possibility to determine the apparent activation energy.（ Ea ） of this transition according to Flory＇s gelation theory. The non-equilibrium thermodynamic fluctuation theory was used to predict the transition behavior. The isothermal transition experiments on hybrid sols with different TEOS（tetraethyl orthosilicate） contents were carried out. The results show that the Ea of a hybrid sol is higher than that of a non- hybrid sol of a TEOS-water-ethanol system. The increasing of TEOS content in a hybrid sol has no obvious effect on the Ea value, but it can enhance the sol-gel .reaction rate.

WEAR TRANSITIONS OF C/Cu COMPOSITE MATERIALS

An unlubricated sliding friction test on C/Cu composite materials is described. The result of the test proves that adhesive wear is the domination. At a certain speed, when the load upon the test block is light, the wear rate remains low level and the friction pair has a good antifriction performance. But when the load increases to a certain value, the wear transitions happen, the wear becomes severe.

Influence of cerium ions on the anatase-rutile phase transition of TiO_2 prepared by sol-gel auto-igniting synthesis

The anatase-rutile phase transformation of TiO_2 doped cerium up to 5 molpercent was studied by X-ray diffraction and X-ray photoelectron spectroscopy. The samples wereprepared by sol-gel auto-igniting synthesis process from a TiO(NO_3)_2-Ce(NO_3)_2-NH_4NO_3-citricacid complex compound system. The combusted amorphous powders were calcined at differenttemperatures. Significant structural changes were observed during the various stages of the phasetransformation. It was concluded that at low dopant contents, cerium ions were incorporated into theTiO_2 structure, and the anatase phase was stabilized; but at larger amounts, part of the dopantwas segregated on the surface of TiO_2 and the rutile formation was accelerated at elevatedcalcination temperature.

Beyond Graphene Anode Materials for Emerging Metal Ion Batteries and Supercapacitors

Intensive research effort is currently focused on the development of efficient, reliable, and environmentally safe electrochemical energy storage systems due to the ever-increasing global energy storage demand. Li ion battery systems have been used as the primary energy storage device over the last three decades. However, low abundance and uneven distribution of lithium and cobalt in the earth crust and the associated cost of these materials, have resulted in a concerted effort to develop beyond lithium electrochemical storage systems. In the case of non-Li ion rechargeable systems, the development of electrode materials is a significant challenge, considering the larger ionic size of the metal-ions and slower kinetics. Two-dimensional(2D) materials, such as graphene, transition metal dichalcogenides, MXenes and phosphorene, have garnered significant attention recently due to their multi-faceted advantageous properties: large surface areas, high electrical and thermal conductivity, mechanical strength, etc. Consequently, the study of 2D materials as negative electrodes is of notable importance as emerging non-Li battery systems continue to generate increasing attention. Among these interesting materials, graphene has already been extensively studied and reviewed, hence this report focuses on 2D materials beyond graphene for emerging non-Li systems. We provide a comparative analysis of 2D material chemistry, structure, and performance parameters as anode materials in rechargeable batteries and supercapacitors.

Recent Progress of Two-Dimensional Thermoelectric Materials

Thermoelectric generators have attracted a wide research interest owing to their ability to directly convert heat into electrical power.Moreover,the thermoelectric properties of traditional inorganic and organic materials have been significantly improved over the past few decades.Among these compounds,layered two-dimensional(2D)materials,such as graphene,black phosphorus,transition metal dichalcogenides,IVA–VIA compounds,and MXenes,have generated a large research attention as a group of potentially high-performance thermoelectric materials.Due to their unique electronic,mechanical,thermal,and optoelectronic properties,thermoelectric devices based on such materials can be applied in a variety of applications.Herein,a comprehensive review on the development of 2D materials for thermoelectric applications,as well as theoretical simulations and experimental preparation,is presented.In addition,nanodevice and new applications of 2D thermoelectric materials are also introduced.At last,current challenges are discussed and several prospects in this field are proposed.

The phase transition, hygroscopicity, and thermal expansion properties of Yb_(2-x)Al_xMo_3O_(12)

Materials with the formula Yb2-xAlxMo3O12 （x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, 0.9, 1.0, 1.1, 1.3, 1.5, and 1.8） were synthesized and their structures, phase transitions, and hygroscopicity investigated using X-ray powder diffraction, Raman spectroscopy, and thermal analysis. It is shown that Yb2-xAlxMo3012 solid solutions crystallize in a single monoclinic phase for 1.7 〈 x 〈 2.0 and in a single orthorhombic phase for 0.0 〈 x 〈 0,4, and exhibit the characteristics of both monoclinic and orthorhombic structures outside these compositional ranges. The monoclinic to orthorhonlbic phase transition temperature of A12Mo3012 can be reduced by partial substitution of A13＋ by Yb3＋, and the Yb2-zAlxMo3012 （0.0 〈 x 〈 2.0） materials are hydrated at room temperature and contain two kinds of water species. One of these interacts strongly with and hinders the motions of the polyhedra, while the other does not. The partial substitution of A13＋ for Yb3＋ in Yb2Mo3012 decreases its hygroscopicity, and the linear thermal expansion coefficients after complete removal of water species are measured to be -9.1 x 10-6/K, -5.5 x 10-6/K, 5.74 x 10-6/K, and 9.5 x 10 6/K for Ybl.sAlo.2（MoO4）3, Yb1.6Alo.4（MoO4）3, Ybo.4All.6（Mo04）3, and Ybo.2Al1.8（MoO4）3, respectively.

Memristive Devices Based on Two-Dimensional Transition Metal Chalcogenides for Neuromorphic Computing

Two-dimensional(2D)transition metal chalcogenides(TMC)and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices,particularly futuristic memristive and synaptic devices for brain-inspired neuromorphic computing systems.The distinct properties such as high durability,electrical and optical tunability,clean surface,flexibility,and LEGO-staking capability enable simple fabrication with high integration density,energy-efficient operation,and high scalability.This review provides a thorough examination of high-performance memristors based on 2D TMCs for neuromorphic computing applications,including the promise of 2D TMC materials and heterostructures,as well as the state-of-the-art demonstration of memristive devices.The challenges and future prospects for the development of these emerging materials and devices are also discussed.The purpose of this review is to provide an outlook on the fabrication and characterization of neuromorphic memristors based on 2D TMCs.

Suppressing irreversible phase transition and enhancing electrochemical performance of Ni-rich layered cathode LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) by fluorine substitution

Ni-rich layered oxide LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)(x≥0.8)is the most promising cathodes for future high energy automotive lithium-ion batteries.However,its application is hindered by the undesirable cycle stability,mainly due to the irreversible structure change at high voltage.Herein,we demonstrate that F substitution with the appropriate amount(1 at%)is capable for improve the electrochemical performance of LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2) cathode significantly.It is revealed that F substitution can reduce cation mixing,stabilize the crystal structure and improve Li transport kinetics.The resulted LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(1.99)F_(0.01)cathode can deliver a high capacity of 194.4 mAh g^(-1) with capacity retention of 95.5%after 100 cycles at 2 C and 165.2 mAh g^(-1) at 5 C.In-situ synchrotron X-ray technique proves that F ions in the cathode materials can suppress the irreversible phase transition from H2 phase to H3 phase in high voltage region by preventing oxygen gliding in a-b planes,ensuring a long-term cycle stability.

Recent progress and prospective on layered anode materials for potassium-ion batteries

Potassium-ion batteries(PIBs),also known as“novel post-lithium-ion batteries,”have promising energy storage and utilization prospects due to their abundant and inexpensive raw materials.Appropriate anode materials are critical for realizing high-performance PIBs because they are an important component determining the energy and power densities.Two-dimensional(2D)layered anode materials with increased interlayer distances,specific surface areas,and more active sites are promising candidates for PIBs,which have a high reversible capacity in the energetic pathway.In this review,we briefly summarize K+storage behaviors in 2D layered carbon,transition metal chalcogenides,and MXene materials and provide some suggestions on how to select and optimize appropriate 2D anode materials to achieve ideal electrochemical performance.

Catalyst activation: Surface doping effects of group Ⅵ transition metal dichalcogenides towards hydrogen evolution reaction in acidic media

Two-dimensional(2D) transition metal dichalcogenides(TMDs) have emerged as promising alternatives to the platinum-based catalysts for hydrogen evolution reaction(HER). The edge site of these2D materials exhibits HER-active properties, whereas the large-area basal plane is inactive.Therefore, recent studies and methodologies have been investigated to improve the performance of TMD-based materials by activating inactive sites through elemental doping strategies. In this review,we focus on the metal and non-metal dopant effects on group VI TMDs such as MoS_(2) MoSe_(2) WS_(2)and WSe_(2) for promoting HER performances in acidic electrolytes. A general introduction to the HER is initially provided to explain the parameters in accessing the catalytic performance of dopedTMDs. Then, synthetic methods for doped-TMDs and their HER performances are introduced in order to understand the effect of various dopants including metallic and non-metallic elements. Finally, the current challenges and future opportunities are summarized to provide insights into developing highly active and stable doped-TMD materials and valuable guidelines for engineering TMD-based nanocatalysts for practical water splitting technologies.

Theoretical investigation on near-infrared and visible absorption spectra of nanometallic aluminium with oxide coating in nanoenergetic materials:size and shape effects

The effects of metal core dimension, oxide shell thickness and ellipsoid aspect ratio of Al-Al2O3 core-shell nanoparticles on the near-infrared and visible absorption spectra of nanocomposite Al-Al2O3/nitrocellulose（NC） film are investigated by numerical calculations. Both the size-dependent interband transitions and frequency-dependent free electron damping of the nanometallic aluminium are taken into account in the calculations. Oxidation effect of nanoaluminium is also analysed. It is shown that oxidation may enhance but may also reduce the optical absorption, depending on the excited light energy and initial dimension of nanoparticle. Metal core size and excited light energy dominate the absorption characteristic. The absorption ability of ellipsoidal nanoparticles is larger than that of spheroidal nanoparticles and increases by the square index as the aspect ratio increases. These calculations will provide some significant theoretical guidance for the preparation and laser ignition of nanoenergetic materials.

Powder Metallurgical Fabrication and Microstructural Investigations of Aluminum/Steel Functionally Graded Material

Aluminum/steel electric transition joints (ETJs) are used in aluminum reduction cell for the purpose of welding aluminum rod and steel bracket components. Solid state welding process used for joining aluminum and steel at the electric transition joints have the drawbacks of cracking and separation at the interface surfaces. Cracking and separation at the electric transition joints are caused by the stress singularities that developed due to the mismatch in thermal and mechanical properties of each material. To overcome the drawback of electric transition joints, aluminum/steel functionally graded may be used as electric transition joints or proposed. Therefore manufacturing and investigation of aluminum/steel functionally graded materials fabricated by powder metallurgy process were carried out through the current work. Different samples with different layers of aluminum/steel functionally graded materials were compacted using steel die and punch at the same compacted pressure and sintered temperature. After investigating the different samples of aluminum/steel functionally graded materials under different fabrication conditions, the suitable fabrication regime was determined with the aid of microscopic observations.

Self-transforming stainless-steel into the next generation anode material for lithium ion batteries

Here,an extremely cost-effective and simple method is proposed in order to morphologically selftransform stain less steel from a completely inactive material to a fully operati onal,nanowire-structured,3D anode material for lithium ion batteries.The reagentless process of a single heating step of the plain stainless steel in a partially reduci ng atmosphere,converts the stain less steel into an active anode via metal-selective oxidation,creating vast spinel-structured nanowires directly from the electrochemically in active surface.The simple process allows the complete utilizati on of the 3D mesh structure as the electrochemically-active spinel nanowires greatly enhance the active surface area.The novel material and architecture exhibits high capacities(-1000 mAh/g after-400 cycles),long cycle life(>1100 cycles)and fast rate performance(>2C).Simple modulation of the substrate can result in very high areal and volumetric capacities.Thus,areal capacities greater than 10 mAh/cm^(2) and volumetric capacities greater than 1400 mAh/cm^(3) can be achieved.Using the proposed method,the potential reduction in cost from the use of battery-grade graphite is at least an order of magnitude,with considerable better results achieved in terms of capacity and intrinsic structural benefits of the substrate,which include direct contact of the active material with the current collector,lack of delamination and binder-free performance.This work provides a new paradigm and a key step in the long route to replace the commercial graphite anode as the next-geneation anode material.

Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Precisely quantifying transition metal(TM) redox in bulk is a key to understand the fundamental of optimizing cathode materials in secondary batteries. At present, the commonly used methods to probe TM redox are hard X-ray absorption spectroscopy(hXAS) and soft X-ray absorption spectroscopy(sXAS).However, they are both facing challenges to precisely quantify the valence states of some transition metals such as Mn. In this paper, Mn-L iPFY(inverse partial fluorescence yield) spectra extracted from Mn-L m RIXS(mapping of resonant inelastic X-ray scattering) is adopted to quantify Mn valence states. Mn-L i PFY spectra has been considered as a bulk-sensitive, non-distorted probe of TM valence states.However, the exact precision of this method is still unclear in quantifying practical battery electrodes.Herein, a series of LiMn_(2)O_(4) electrodes with different charge and discharge states are prepared. Based on their electrochemical capacity(generally considered to be very precise), the precision of Mn iPFY in quantifying bulk Mn valence state is confirmed, and the error range is unraveled. Mn-L mRIXS iPFY thus is identified as one of the best methods to quantify the bulk Mn valence state comparing with hXAS and sXAS.

Perovskite-transition metal dichalcogenides heterostructures: recent advances and future perspectives

Transition metal dichalcogenides(TMDs)and perovskites are among the most attractive and widely investigated semiconductors in the recent decade.They are promising materials for various applications,such as photodetection,solar energy harvesting,light emission,and many others.Combining these materials to form heterostructures can enrich the already fascinating properties and bring up new phenomena and opportunities.Work in this field is growing rapidly in both fundamental studies and device applications.Here,we review the recent findings in the perovskite-TMD heterostructures and give our perspectives on the future development of this promising field.The fundamental properties of the perovskites,TMDs,and their heterostructures are discussed first,followed by a summary of the synthesis methods of the perovskites and TMDs and the approaches to obtain high-quality interfaces.Particular attention is paid to the TMD-perovskite heterostructures that have been applied in solar cells and photodetectors with notable performance improvement.Finally through our analysis,we propose an outline on further fundamental studies and the promising applications of perovskite-TMD heterostructures.

Nanoindentation Characteristics of Cement Paste and Interfacial Transition Zone in Mortar with Rice Husk Ash

The nanostructure of cementitious materials has important effects on concrete properties. The effects of rice husk ash（RHA） on cement hydration product phases and interfacial transition zone（ITZ） in mortar were investigated from the nano-scale structure perspective. The experimental results indicate that, with the increase of RHA dosages of samples, the volume fraction of high-density calcium-silicate-hydrate（HD C-S-H） in porosity and hydration product phases increases. The volume fractions of HD C-S-H in C-S-H of samples show an increasing trend with the increase of RHA dosages. RHA decreases the thickness of ITZ and increases the matrix elastic moduli of samples, however, the RHA dosoges hardly affect the thickness and elastic moduli.